CN111220693A - Hetian jade identification method for different producing areas based on multi-element content statistics - Google Patents
Hetian jade identification method for different producing areas based on multi-element content statistics Download PDFInfo
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- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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Abstract
The invention discloses a Hetian jade identification method based on multi-element content statistics, which comprises the following steps: s1, crushing and grinding the Hetian jade sample to obtain Hetian jade powder; s2, dissolving the Hetian jade powder by using hydrofluoric acid and nitric acid to obtain a dissolved solution; s3, detecting elements in the dissolving solution by adopting an inductively coupled plasma mass spectrometry method to obtain an element detection result; and S4, analyzing the element detection result to obtain an analysis result, establishing a Hetian jade producing area prediction model according to the analysis result, and identifying the producing area of the Hetian jade according to the Hetian jade producing area prediction model. The method can provide a scientific measurement method for determination of trace elements and rare earth elements in Hetian jade in different areas, and simultaneously provides a certain data basis for true and false identification and origin tracing of Hetian jade.
Description
Technical Field
The invention relates to the technical field of Hetian jade identification, in particular to a Hetian jade identification method based on multi-element content statistics.
Background
The main origins of Hetian jade are Xinjiang, Qinghai and Russia in China. Hetian jade produced in Xinjiang has been popular with the market and consumers. For a long time, the method is mainly characterized in that the method distinguishes the nephrite in different producing areas by naked eyes, and has strong subjectivity and uncertainty; at present, no research on the identification of Hetian jade samples in different producing areas is reported, so how to scientifically identify the Hetian jade producing area is an urgent problem to be solved for identifying the gem and jade.
Disclosure of Invention
The invention aims to solve the problems and provides a nephrite jade identification method based on multi-element content statistics, which is simple to operate and accurate in result.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for identifying Hetian jade in different producing areas based on multi-element content statistics comprises the following steps:
s1, crushing and grinding the Hetian jade sample to obtain Hetian jade powder;
s2, dissolving the Hetian jade powder by using hydrofluoric acid and nitric acid to obtain a dissolved solution;
s3, detecting elements in the dissolving solution by adopting an inductively coupled plasma mass spectrometry method to obtain an element detection result;
and S4, analyzing the element detection result to obtain an analysis result, establishing a Hetian jade producing area prediction model according to the analysis result, and identifying the producing area of the Hetian jade according to the Hetian jade producing area prediction model.
Further, the particle size of the nephrite jade powder in the step S1 is less than 74 μm.
Further, the specific operation steps of step S2 are as follows:
s21, weighing 0.05g of Hetian jade powder, placing the Hetian jade powder in a polytetrafluoroethylene digestion tank, wetting the polytetrafluoroethylene digestion tank, adding 2mL of nitric acid and 2mL of hydrofluoric acid, covering and sealing a steel sleeve, and placing the polytetrafluoroethylene digestion tank in a constant-temperature oven at 190 ℃ for 48 hours;
s22, taking out, putting on an electric heating plate, evaporating until 1-2 drops are left, adding 2mL of nitric acid and 2mL of hydrofluoric acid for the second time, putting on the electric heating plate, and evaporating until 1-2 drops are left;
s23, adding 2mL of nitric acid and 2mL of hydrofluoric acid for the third time, covering and sealing a steel sleeve, and placing in a constant-temperature oven at 190 ℃ for 12-24 hours;
and S24, taking out, putting on an electric heating plate, evaporating until 1-2 drops are left, cooling, transferring into a 100mL volumetric flask, and fixing the volume by using 2% nitric acid.
Further, in the step S3, when the element in the solution is detected, the measurement is performed three times, and the measurement result is the average value thereof.
Further, the analyzing of the element detection result in step S4 includes analyzing the content of multiple elements in the nephrite sample in different areas, analyzing the main components of multiple elements in the nephrite sample in different areas, and analyzing the LDA discrimination of the nephrite sample in different areas.
Compared with the prior art, the invention has the advantages and positive effects that:
the hydrofluoric acid-nitric acid dissolving method provided by the invention can dissolve a large amount of samples at one time, and has the advantages of high efficiency, good dissolving effect and simple operation; and the inductively coupled plasma mass spectrometry is adopted to detect trace elements in the Xinjiang Hetian jade, has the advantages of low detection limit, high accuracy, good selectivity, high analysis speed, wide application range and the like, and can meet the detection work of a large number of Xinjiang Hetian jade. The method can provide a scientific measurement method for determination of trace elements and rare earth elements in Hetian jade in different areas, and simultaneously provides a certain data basis for true and false identification and origin tracing of Hetian jade.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a graphical representation of the standardized REE partitioning pattern for different regions of Hetian jade spherule siderite.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
The production areas of the Hetian jade can be identified by testing and analyzing the types and the contents of trace components of the Hetian jade due to slight differences of chemical composition components caused by different environments of the Hetian jade in different production areas. The implementation steps of the invention are as follows:
1. preparation of the samples
The sample was prepared by grinding to a particle size of less than 74 μm (200 mesh) and drying.
2. Preparation of sample solution
Accurately weighing 0.05g (accurate to 0.0001g) of Hetian jade sample powder in a polytetrafluoroethylene digestion tank, wetting with a small amount of water, adding 2mL of nitric acid and 2mL of hydrofluoric acid, covering and sealing with a steel sleeve, placing in a constant-temperature oven at 190 ℃ for 48h, taking out, placing on an electric hot plate to evaporate to be nearly dry, then respectively adding 2mL of nitric acid and 2mL of hydrofluoric acid, evaporating to be nearly dry again, adding 2mL of acid and 2mL of hydrofluoric acid again, covering and sealing with a steel sleeve, placing in the oven to keep the temperature for 12-24 h, taking out, evaporating to be nearly dry again on the electric hot plate, cooling, transferring into a 100mL bottle, fixing the volume with 2% of nitric acid, and measuring the volume.
3. Number of measurements
The same sample was measured independently three times, and the results were averaged.
4. Blank test
For each run, two blanks should be analyzed in parallel with the sample under the same conditions.
5. Drawing working curve
Optimized tuning of instrument → curve measurement of standard sample → measurement of unknown sample → preliminary arrangement of data → calculation of analytical result → precision (repeatability and reproducibility)
Laboratory apparatus
NexION model 300X inductively coupled plasma mass spectrometer (PerkinElmer, USA); Milli-RIOS30 based ultrapure water meter (Millipore, USA); HXN-1 type far infrared constant temperature drying oven (Zhejiang Yu City Hongxing mechanical instruments manufacturing Co., Ltd.); an EH35 model micro-control digital display electric heating plate (Leibetake Co., Ltd.); an XP205DR model balance (Mettlert Torlo).
Sample and principal reagent
Taking representative Hetian jade samples in the collected samples as research objects, 45 batches of Hetian jade samples in Korea, Russia, Qinghai, Xinjiang and other places are collected; nitric acid and hydrofluoric acid are both superior grade pure, and become a chemical reagent factory of Syngnathus; multielement mixed standard stock solution (containing 20 elements to be determined by experiment, 10mg/L), Shanghai city research institute of metrological testing technology; the multi-element rare earth standard stock solution (comprising 16 elements such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, terbium, holmium, erbium, thulium, ytterbium, lutetium and the like, 1000 mu g/mL) and the national analysis and test center for nonferrous metals and electronic materials; standard stock solution of internal standard elements Li, Sc, Ge, In, Bi, Tb, Rh and 10 mug/mL, and national analysis and test center for nonferrous metals and electronic materials; tuning solution Be, Ce, Fe, In, Li, Mg, Pb, U, 1. mu.g/L, PerkinElmer, USA.
Working conditions of the apparatus
The working parameters of ICP-MS are optimized daily by using tuning liquid, so that the indexes of instrument sensitivity, oxide, double electric charges, resolution ratio and the like reach the best, and the working conditions of the instrument are as follows: the radio frequency power is 1200W, the flow rate of atomizing air is 1.0L/min, the flow rate of auxiliary gas is 1.0L/min, the flow rate of plasma gas is 16.0L/min, the scanning mode is peak jump, the integration time is 0.5s, the sampling depth is 7mm, and the rotating speed of a peristaltic pump is 20 r/min.
Data analysis
The data were subjected to differential analysis, cluster analysis, Fisher discriminant analysis, and principal component analysis using SPSS23.0 software, OriginPro2016 for mapping. In Fisher discrimination and PLS-DA analysis, 40 samples are randomly selected as a training set, and a prediction model is established; the remaining 15 samples were used as validation sets and the accuracy of the model built was analyzed using external tests.
Results and analysis
Analysis of contents of multiple elements in Hetian jade samples in different regions
The ICP-MS was used to measure 45 Hetian jade samples from 4 provinces, and the content of 36 elements was obtained (Table 1). In order to know the difference of element compositions in nephrite samples in different regions, element indexes related to the regions are screened, and single-factor variance analysis is carried out on the contents of 36 elements in nephrite in different provinces. The results (table 1) show that: the content of Al, Fe, Ti, Co, Ni, Cu, Sr, Ba, B, As, V, Pb, La, Y, Sc, Nd, Sm, Eu and other elements is obviously different between different producing areas and field jade (P < 0.05). The explanation can utilize multiple elements to establish a discriminant analysis model of the Hetian jade regional source.
TABLE 1 elemental content of Hetian jade in different regions
T test on the multi-element content of nephrite samples in different production areas shows that the content of Na, Al, K, Ca, Sc, V, rare earth elements and other elements in different areas are remarkably different among areas (P is less than 0.05).
Analysis of main components of multiple elements in Hetian jade samples in different regions
PCA refers to a multivariate statistical analysis (MVA) method that passes multidimensional variables through linear transformations to select fewer important variables. The PCA is to perform linear data conversion and dimensionality reduction on information of a plurality of variables on the premise of keeping original main information, perform linear classification on dimensionality-reduced data, and finally display the overall quality difference between samples on a scatter diagram of the PCA. The PC1 (1 st principal component) and the PC2 (2 nd principal component) include the contribution rates of the PC1 and the PC2 obtained in the PCA conversion, and the larger the contribution rate is, it is demonstrated that the principal components (PAs) can better reflect the original multi-index information.
In order to compress a large amount of information represented by 36 elements in the Hetian jade samples of different producing areas into a few main components, the distribution situation of the different elements in space and characteristic elements in the Hetian jade samples of different areas are known, and the main component analysis is carried out on 36 elements in 45 Hetian jade samples of 4 producing areas, and the results are shown in Table 2. Selecting components with characteristic values larger than 1 as principal components to obtain 5 principal components, wherein the cumulative variable reaches 98.189%, the first principal component contribution rate is 49.278%, the second principal component contribution rate is 23.253%, the third principal component contribution rate is 13.559%, the fourth principal component contribution rate is 6.774%, the fifth principal component contribution rate is 5.326%, the 1 st principal component and the 2 nd principal component represent 72.53% of the variable, the 3 rd principal component and the 4 th principal component represent 20.33% of the variable, and the load values of the first 5 principal components of 36 elements in the Tianyu are shown in Table 3. In the 1 st main component, rare earth elements such as Y, Ce, Tb, Tm, La, Lu, Gd, Yb, Dy and the like have higher load values; in the 2 nd main component, elements such as Co, Cu, Zn, K, Li, Mg, Mn and the like have higher load values; in the 3 rd main component, As, Ba, Fe, Ni, V, Sr, Cr and other elements have higher load values; in the 4 th main component, elements such as Na and Sc have high load values. The first 4 principal components contain 92.86% of the total variance of the interpretation, which can sufficiently achieve the purpose of reflecting the original data information. In the fifth main component, elements such as Cu have higher load values, so that the characteristic elements in nephrite samples in different areas can be considered as Ca, Co, Fe, Rb, Zn, Mg, Cu, Cd, Ba, Sm, rare earth elements and the like.
Table 236 element content principal component analysis results
Table 336 principal component contribution values of the element indexes
LDA discriminant analysis of Hetian jade samples in different areas
LDA is a conventional pattern recognition and sample classification method, which is often applied to statistical analysis, pattern recognition and machine learning, and mainly finds a linear relationship between a predictor variable X and a classifier variable Y, usually projects a high-dimensional pattern sample to an optimal discrimination vector space to achieve the effects of extracting classification information and compressing feature space dimensions, and ensures that the pattern sample has the maximum inter-class distance and the minimum intra-class distance in a new subspace after projection, i.e., the criterion for screening variables by this method is to maximize the difference between classes and minimize the difference within classes, so as to obtain the best separability of the pattern in the space. Firstly, the model sample is judged back by using the total verification and the interactive verification of the discriminant analysis so as to verify the discriminant effect. The interactive verification method is often used to obtain a higher misjudgment rate than the overall verification method, and the credibility of the return judgment result is higher.
The experiment performed a total validation and an interactive validation on 20 modeled samples. The results are shown in Table 4. The element contents in the Hetian jade samples of different producing areas are used as LDA analysis objects, the total verification discrimination rates of the Hetian jade samples of different producing areas are respectively 100% and 100%, and the interactive verification discrimination rates are respectively 100% and 94.44%. The result shows that Al, As, Ba, Cd, Ca, Cu, Fe, Mg, Zn and Mn in Hetian jade and rare earth elements are effective indexes for identifying the origin places of Hetian jade, thereby providing important basis for establishing geographical signs and origin place protection of Hetian jade in different areas.
TABLE 4 LDA determination results of Hetian jade elements in different producing areas
The content of the multi-element data of the Hetian jade is different among small-range areas by performing difference analysis on the multi-element content data of the sampled Hetian jade. On the basis of applying Fisher function and cross inspection, a gradual discrimination method is adopted for discrimination analysis, so that the purpose of accurately tracing the source in a small-range region is achieved, and the correct discrimination rate reaches 100%. And the characterization index of tracing is obtained and verified through the principal component analysis and discriminant analysis of the multi-element content in the sampled Tianyu. In the results obtained by the principal component analysis, the first principal component mainly comprises 6 elements of Zn, K, Mg, Na, Ca and Mn according to the contribution size, and the second principal component mainly comprises 3 elements of Cd, Cu and Fe according to the contribution size; and comprehensively analyzing and selecting 6 elements of K, Zn, Mg, Na, Ca and Mn as the traceability indexes of multiple elements in the Tianyu. The results of the discrimination and verification of different producing areas show that Zn, K, Mg, Na, Ca, Mn and rare earth elements can be used as multi-element tracing characterization indexes for tracing in different areas.
Due to different geochemical condition characteristics of the output environment, the types and the contents of the rare earth elements show different characteristics. Relatively, the previous studies have been less studied for REE (rare earth element).
The REE family has relatively similar physicochemical properties. However, as the atomic number increases, their ionic radii tend to decrease, which results in differences in their chemical properties. And (3) carrying out spherulite meteorite standardization according to the REE value of the sample, and respectively obtaining REE partition charts of the tail part, the root part, the notopterygium part, the farmland and the four places of the leaf city by taking the spherulite meteorite value of the REE content standard as an ordinate and taking the atomic number as an abscissa.
The calculation formula of delta Eu is as follows:
wherein Eu is element europium; sm is element samarium; gd is element gadolinium;
if delta Eu is larger than 1.05, the positive abnormality is called; if delta Eu is less than 0.95, a negative anomaly is identified.
As shown in fig. 1, the samples of both the end and leaf cities in the graph exhibited a tendency toward a decrease in Light Rare Earth Elements (LREE) and also exhibited a δ Eu negative anomaly. In YC, the difference between LREE and Heavy Rare Earth Element (HREE) is obvious, the HREE is enriched, and delta Eu is negative anomaly and is 0.47. The content of QM and YT rare earth elements is low, delta Eu is 0.38-0.65, the delta Eu is a medium negative anomaly, and the distribution mode of the delta Eu is relatively flat. The LREE and HREE are not very distinct.
ICP-MS is used for carrying out full quantitative analysis on 15 elements in the digestion solution, and the determination results are shown in Table 4.
By analyzing the change trend chart of the rare earth elements, the distribution types of the non-regional Hetian jade are relatively similar: the light rare earth is of a gentle right-leaning type and belongs to a light rare earth enrichment type; severe loss of Tm occurs; meanwhile, obvious negative abnormality of Eu occurs, and the RQ is supposed to be negative abnormality of delta Eu in view of distribution type. The δ Eu value of RQ is 0.74, the δ Eu value of QM is 0.65, the δ Eu value of YT is 0.38, and the δ Eu value of YC is 0.47.
Aiming at the characteristics that the Hetian jade has complex components and is difficult to completely digest by a high-pressure closed conventional acid dissolution system, the feasibility and the advantages of processing methods such as hydrofluoric acid-nitric acid high-pressure closed digestion, nitric acid redissolution, nitric acid extraction and the like are confirmed, the Hetian jade sample is completely digested, and the content of rare earth elements in the Hetian jade sample is accurately determined by ICP-MS. The method has the advantages of low acid consumption and low blank value, greatly reduces energy consumption compared with other traditional methods, improves analysis efficiency, can quickly determine the rare earth elements in the Hetian jade sample, and provides reference for analysis of the rare earth elements in other ore jades.
The pressurized closed acid dissolution method is obviously improved compared with the normal-pressure four-acid sample dissolution method. The method adopts HF-HNO3The sample is dissolved for a long time at high temperature and high pressure, so that the complete decomposition of most of indissolvable elements is ensured, and simultaneously volatile elements cannot be lost under a sealed condition. Because the acid does not volatilize in the sample dissolving process and repeatedly flows back in the system, the sample decomposition can be completed only by using a small amount of purified acid, and the possibility of environmental pollution is greatly reduced, thereby ensuring a low blank value.
By using HF + HNO3The method for dissolving the sample by sealing dissolution can not only ensure the complete dissolution of the sample, but also has the obvious advantages compared with the alkali melting method, namely that the method does not carry any metal ions, and simultaneously has HF and HNO3Easy purification and little pollution, thus low analysis background and low determination limit.
The method solves the problem that the conventional Hetian jade cannot be completely digested to cause inaccurate test results, realizes accurate determination of the rare earth elements in the Hetian jade, and is favorable for providing a basis for researching the cause of the Hetian jade and finding ores subsequently. The distribution mode characteristics of the rare earth elements of the Hetian jade in different areas are analyzed, right-leaning light rare earth is enriched, and the preliminarily discussed rare earth element abundance characteristics can provide a basis for researching the cause of the Hetian jade deposit in the main production area.
The internal standard method is applied to the quantitative analysis of ICP-MS, so that the general matrix effect is effectively compensated, and the short-term drift and the long-term drift of an analysis signal are monitored and corrected, so that the accuracy of an analysis result is improved.
The inductively coupled plasma mass spectrometry has the advantages of low detection limit, high accuracy, high analysis speed and wide application. The method has accurate result, can detect a large amount of samples or a small amount of samples, and has wide application range. The detection limit of the method is lower than one twentieth of the national standard method, and the precision of the method is improved by 3 times.
Claims (5)
1. A method for identifying Hetian jade in different producing areas based on multi-element content statistics is characterized by comprising the following steps: the method comprises the following steps:
s1, crushing and grinding the Hetian jade sample to obtain Hetian jade powder;
s2, dissolving the Hetian jade powder by using hydrofluoric acid and nitric acid to obtain a dissolved solution;
s3, detecting elements in the dissolving solution by adopting an inductively coupled plasma mass spectrometry method to obtain an element detection result;
and S4, analyzing the element detection result to obtain an analysis result, establishing a Hetian jade producing area prediction model according to the analysis result, and identifying the producing area of the Hetian jade according to the Hetian jade producing area prediction model.
2. The method for distinguishing nephrite jade species of different origins based on the statistics of the contents of multiple elements as claimed in claim 1, wherein: the particle size of the nephrite jade powder in the step S1 is less than 74 μm.
3. The method for distinguishing nephrite jade species of different origins based on the statistics of the contents of multiple elements as claimed in claim 2, wherein: the specific operation steps of step S2 are as follows:
s21, weighing 0.05g of Hetian jade powder, placing the Hetian jade powder in a polytetrafluoroethylene digestion tank, wetting the polytetrafluoroethylene digestion tank, adding 2mL of nitric acid and 2mL of hydrofluoric acid, covering and sealing a steel sleeve, and placing the polytetrafluoroethylene digestion tank in a constant-temperature oven at 190 ℃ for 48 hours;
s22, taking out, putting on an electric heating plate, evaporating until 1-2 drops are left, adding 2mL of nitric acid and 2mL of hydrofluoric acid for the second time, putting on the electric heating plate, and evaporating until 1-2 drops are left;
s23, adding 2mL of nitric acid and 2mL of hydrofluoric acid for the third time, covering and sealing a steel sleeve, and placing in a constant-temperature oven at 190 ℃ for 12-24 hours;
and S24, taking out, putting on an electric heating plate, evaporating until 1-2 drops are left, cooling, transferring into a 100mL volumetric flask, and fixing the volume by using 2% nitric acid.
4. The method for distinguishing nephrite jade species of different origins based on the statistics of the contents of multiple elements as claimed in claim 3, wherein: in the step S3, the elements in the solution are measured three times, and the average value of the measurement results is obtained.
5. The method of distinguishing Hetian jade from different origins based on multi-element content statistics as claimed in claim 4, wherein: the analyzing of the element detection result in the step S4 includes analyzing the content of a plurality of elements in the nephrite sample in different areas, analyzing the main components of a plurality of elements in the nephrite sample in different areas, and analyzing the LDA discrimination of the nephrite sample in different areas.
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